EP3852921A1 - Catalyst system for producing cyclic carbonates and method related thereto - Google Patents
Catalyst system for producing cyclic carbonates and method related theretoInfo
- Publication number
- EP3852921A1 EP3852921A1 EP19842424.4A EP19842424A EP3852921A1 EP 3852921 A1 EP3852921 A1 EP 3852921A1 EP 19842424 A EP19842424 A EP 19842424A EP 3852921 A1 EP3852921 A1 EP 3852921A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- catalyst system
- carbon atoms
- independently selected
- catalyst
- compound
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 88
- 150000005676 cyclic carbonates Chemical class 0.000 title claims abstract description 30
- 238000000034 method Methods 0.000 title claims description 81
- 150000001875 compounds Chemical class 0.000 claims abstract description 68
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 57
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 43
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 43
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 35
- 239000012041 precatalyst Substances 0.000 claims abstract description 34
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 17
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 17
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 17
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 17
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims abstract description 16
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 16
- 125000001072 heteroaryl group Chemical group 0.000 claims abstract description 14
- 150000004820 halides Chemical class 0.000 claims abstract description 12
- 125000003118 aryl group Chemical group 0.000 claims abstract description 11
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 35
- 150000001412 amines Chemical class 0.000 claims description 25
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 25
- 239000003960 organic solvent Substances 0.000 claims description 25
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 23
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 22
- 229910052739 hydrogen Inorganic materials 0.000 claims description 21
- 239000001257 hydrogen Substances 0.000 claims description 21
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 19
- 125000003545 alkoxy group Chemical group 0.000 claims description 18
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical group I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 17
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 15
- -1 SiCfr Chemical compound 0.000 claims description 12
- 239000001569 carbon dioxide Substances 0.000 claims description 11
- 238000010992 reflux Methods 0.000 claims description 11
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical group [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 10
- 150000001805 chlorine compounds Chemical group 0.000 claims description 9
- 238000002360 preparation method Methods 0.000 claims description 9
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 229910000077 silane Inorganic materials 0.000 claims description 8
- 238000003746 solid phase reaction Methods 0.000 claims description 6
- 238000010671 solid-state reaction Methods 0.000 claims description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N 1H-imidazole Chemical compound C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 5
- 150000001350 alkyl halides Chemical class 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 229910003930 SiCb Inorganic materials 0.000 claims description 4
- 238000007598 dipping method Methods 0.000 claims description 4
- 238000005470 impregnation Methods 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 125000003944 tolyl group Chemical group 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 claims description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 2
- JHXKRIRFYBPWGE-UHFFFAOYSA-K bismuth chloride Chemical group Cl[Bi](Cl)Cl JHXKRIRFYBPWGE-UHFFFAOYSA-K 0.000 claims description 2
- 150000002118 epoxides Chemical class 0.000 claims 2
- 125000003700 epoxy group Chemical group 0.000 claims 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical group Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims 1
- WGYKZJWCGVVSQN-UHFFFAOYSA-O propan-1-aminium Chemical compound CCC[NH3+] WGYKZJWCGVVSQN-UHFFFAOYSA-O 0.000 claims 1
- PZJJKWKADRNWSW-UHFFFAOYSA-N trimethoxysilicon Chemical group CO[Si](OC)OC PZJJKWKADRNWSW-UHFFFAOYSA-N 0.000 claims 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract description 6
- 230000003197 catalytic effect Effects 0.000 description 18
- 150000002924 oxiranes Chemical class 0.000 description 12
- 239000000126 substance Substances 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 239000000377 silicon dioxide Substances 0.000 description 6
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000011068 loading method Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 238000005119 centrifugation Methods 0.000 description 3
- 238000006352 cycloaddition reaction Methods 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000010414 supernatant solution Substances 0.000 description 3
- VNDYJBBGRKZCSX-UHFFFAOYSA-L zinc bromide Chemical compound Br[Zn]Br VNDYJBBGRKZCSX-UHFFFAOYSA-L 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 238000000498 ball milling Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003426 co-catalyst Substances 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 2
- 239000002608 ionic liquid Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- OOKUTCYPKPJYFV-UHFFFAOYSA-N 1-methyl-1h-imidazol-1-ium;bromide Chemical compound [Br-].CN1C=C[NH+]=C1 OOKUTCYPKPJYFV-UHFFFAOYSA-N 0.000 description 1
- OPWQHYSPLFFRMU-UHFFFAOYSA-N 1-trimethoxysilylpropan-1-amine Chemical compound CCC(N)[Si](OC)(OC)OC OPWQHYSPLFFRMU-UHFFFAOYSA-N 0.000 description 1
- JDIIGWSSTNUWGK-UHFFFAOYSA-N 1h-imidazol-3-ium;chloride Chemical compound [Cl-].[NH2+]1C=CN=C1 JDIIGWSSTNUWGK-UHFFFAOYSA-N 0.000 description 1
- VEUMANXWQDHAJV-UHFFFAOYSA-N 2-[2-[(2-hydroxyphenyl)methylideneamino]ethyliminomethyl]phenol Chemical compound OC1=CC=CC=C1C=NCCN=CC1=CC=CC=C1O VEUMANXWQDHAJV-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- BYQADQLDVPAGSR-UHFFFAOYSA-N toluene;hydrobromide Chemical compound Br.CC1=CC=CC=C1 BYQADQLDVPAGSR-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0292—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature immobilised on a substrate
- B01J31/0295—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature immobilised on a substrate by covalent attachment to the substrate, e.g. silica
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0255—Phosphorus containing compounds
- B01J31/0267—Phosphines or phosphonium compounds, i.e. phosphorus bonded to at least one carbon atom, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, the other atoms bonded to phosphorus being either carbon or hydrogen
- B01J31/0268—Phosphonium compounds, i.e. phosphine with an additional hydrogen or carbon atom bonded to phosphorous so as to result in a formal positive charge on phosphorous
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/08—Silica
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/18—Arsenic, antimony or bismuth
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0235—Nitrogen containing compounds
- B01J31/0239—Quaternary ammonium compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
- B01J31/0279—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the cationic portion being acyclic or nitrogen being a substituent on a ring
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
- B01J31/0281—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member
- B01J31/0284—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member of an aromatic ring, e.g. pyridinium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0298—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature the ionic liquids being characterised by the counter-anions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
- B01J31/121—Metal hydrides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/27—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a liquid or molten state
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/04—Mixing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
- C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
- C07D317/32—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D317/34—Oxygen atoms
- C07D317/36—Alkylene carbonates; Substituted alkylene carbonates
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
- B01J2231/34—Other additions, e.g. Monsanto-type carbonylations, addition to 1,2-C=X or 1,2-C-X triplebonds, additions to 1,4-C=C-C=X or 1,4-C=-C-X triple bonds with X, e.g. O, S, NH/N
Definitions
- This invention relates to a catalyst system for producing cyclic carbonates and a method for preparation of the cyclic carbonates by using the catalyst system.
- Carbon dioxide (CO?) emissions such as from industrial processes and fuel combustion, are becoming a serious problem worldwide because such emissions are considered a primary driver of climate change.
- Global Energy & C0 2 Status Report 2017 launched by the International Energy Agency (TEA)
- TAA International Energy Agency
- CO2 Carbon dioxide
- Legislators around the globe have started to set limitations on the unrestricted release of CO2 in the atmosphere.
- Cyclic carbonates are one of those because they can be easily produced from the cycloaddition of CO? to epoxides under mild conditions.
- Cyclic carbonates are at the center of a multibillion USD market that involves polycarbonates, glycols, and polyesters.
- CO2 is Idnetically and thermodynamically stable, thus it requires a large amount of energy to transform CO? into other chemicals, including cyclic carbonates.
- a promising approach is to develop effective catalysts that allow for higher conversion of CO at lower temperatures.
- Cyclic carbonates are produced from CO? by cycloaddition reaction to epoxides.
- Several catalyst systems exist to carry out such reaction are capable of operating using impure CO2 under ambient or moderate pressure (0.1-1 MPa).
- the ability to capture CO2 from gas mixtures is advantageous as it can be easily applied with flue gas and is therefore commercially attractive for cyclic carbonate production.
- said catalysts include a bimetallic aluminum (salen) complex disclosed in Energy Environ. Sci., 2010,3, 212-215 which is used for cyclic carbonate production with CO2 having moisture and NO x as impurities in CO .
- said complex has a very high molecular weight and its preparation involves several synthetic steps because of the elaborated structure of organic framework-coordinating aluminum atoms.
- US 9,586.926 B2 disclosed a method for producing cyclic carbonate from carbonation of epoxide by CO .
- the method is performed via a homogeneous catalyst system comprising a pre-catalyst selected from YCb, Y2O3, Y(N03)3 > ScCk or La(3 ⁇ 4 and a co-catalyst selected from tefrabutylammonium bromide, 4-dimethylaminopyridine, or bis(triphenylphosphine) iminiirm chloride at a mole ratio in the range of 1 :1 to 1 :2.
- the catalytic activity of this system with impure or diluted CO2 is relatively low under ambient conditions.
- Monteiro, et. al. (Applied Catalysis A: General (2017), 544 (25), 46-54) disclosed a catalyst system comprising l ⁇ meihyl-3-(3-tiimethoxysilylpiOpyI) imidazolium chloride ionic liquid catalyst supported on titanate nanotubes (TNT) or nano wires (TNW) as a pre catalyst and ZnBr2 as a co-catalyst for synthesizing cyclic carbonates. Although selectivity of the catalyst to CO2 is high, this catalyst was not applied for the conversion of impure or diluted CO2.
- the present invention is intended to provide a catalyst system for the conversion of CO? and epoxides to cyclic carbonates under mild conditions using pure and impure CO2 having a high catalytic activity and being cost-effective.
- the present invention provides a catalyst system for producing cyclic carbonates from carbon dioxide (CO?) and epoxide-based compounds comprising: a pre-catalyst selected from the compound having the formula BiX z ; a compound having the formula (I)
- X and Y each independently represent halide:
- R ! , R 2 , and R 3 are independently selected from an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms;
- R 4 , R 5 , and R 6 are independently selected from an alkyl group having 1 to 4 carbon atoms or an aryl group, or R 4 , R ⁇ and R 6 are taken together to form a heteroaryl ring; and a metal oxide support selected from MgO, SiOy ZnO, ARCR or Ti0 2 .
- the present invention relates to a method for preparation of a catalyst system comprising steps of:
- R n , R 12 , and R n are independently selected from an alkyl group having carbon atoms 1 to 4 or an alkoxy group having 1 to 4 carbon atoms.
- step (c) contacting the pre-catalyst with the metal oxide obtained from step (b) for about 1 to 5 hours, wherein a concentration of the pre-catalyst is in the range of about 1 to about 10 % by weight of the metal oxide.
- the present invention relates to a method for preparation of a catalyst system comprising steps of:
- step (b) mixing the product obtained from step (a) with an alky! halide in an organic solvent at a temperature in the range of about 100 to 150 °C for about 12 to 72 hours, wherein the mole ratio between the amine-based compound and the alkyl halide is in the range of about 5:1 to 1 :5; and
- step (c) contacting the pre-catalyst with the metal oxide obtained from step (b) for about 1 to 5 hours, wherein the concentration of the pre-catalyst is in the range of about 1 to 10 % by weight of the metal oxide.
- the present invention relates to a method for producing cyclic carbonates, which comprises reacting epoxide-based compounds with carbon dioxide in the presence of a catalyst system comprising: a pre-catalyst selected from the compound having the formula BiX z ; a compound having the formula (I) where:
- X and Y each independently represent halide
- Rh R 2 , and R 3 are independently selected from an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms:
- R 4 , R 5 , and R 6 are independently selected from an alkyl group having 1 to 4 carbon atoms or an aryl group, or R 4 , R 5 . and R 6 are taken together to form a heteroaryl ring; and a metal oxide support selected from MgO, Si0 2 , ZnO. AbOs , or Ti0 2 wherein said method is performed using the concentration of the catalyst system in the range of about 0.1 to 20 mol% relative to the epoxide-based compounds; at a pressure of carbon dioxide in the range of about 1 to 100 bar; a temperature in the range of about 10 to 200 °C; and a reaction time in the range of about 1 to 8 hours.
- the present i vention provides a catalyst system for producing cyclic carbonates with cost-effectiveness and high catalytic activity for conversion of C0 2 and epoxide-based compounds to cyclic carbona tes. Also, the present invention provides a method of making the cyclic carbonates by using the catalyst system with mild conditions using pure and impure CO?. Details of the present invention can be elucidated according to the specification as follows.
- Equipment, apparatus, methods, or chemicals mentioned here means equipment, apparatus, processes, or chemicals commonly operated or used by those skilled in the art, unless explicitly stated otherwise that they are equipment, apparatus, methods, or chemicals specifically used in this invention.
- compositions and/or processes disclosed and claimed are aimed to include aspects of the invention from actions, operation, modifications, or changing of any parameters without performing significantly different experiments from this invention, and obtaining similar objects with the same utilities and results of the present invention according to persons skilled in the art although without mention of the claims specifically. Therefore, substitution or similar objects to the present invention including minor modifications or changes which can be clearly seen by persons skilled in the art should be considered within the scope, spirit, and concept of the invention as appended claims.
- the present invention provides a catalyst system for producing cyclic carbonates comprising: a pre-catalyst selected from the compound having the formula BiX 3 ⁇ 4 a compound having the formula (I)
- X and Y each independently represent halide
- R 5 , R 2 , and R J are independently selected from an alkyl group having 1 to 4 carbon atoms or an a!koxy group having 1 to 4 carbon atoms;
- R 4 , R: ⁇ and R 6 are independently selected from an alkyl group having 1 to
- R 4 carbon atoms or an aryl group or R 4 , R 5 , and R 6 are taken together to form a heteroaryl ring; and a metal oxide support selected from MgO, Si0 2 , ZnO, AI2O3 , or ⁇ 1O2.
- X is chloride
- the pre-catalyst is BiCR.
- Y is selected from chloride, bromide, or iodide.
- m is 1.
- R 1 , R 2 , and R 3 are independently selected from an alkoxy group having 1 to 4 carbon atoms. Preferably, R 1 , R 2 , and R 3 are methoxy.
- R 4 , R 3 , and R 6 are independently selected from an alkyl group having 1 to 4 carbon atoms.
- R 4 , R 5 , and R 6 are methyl.
- R 4 , R 5 , and R° are taken together to form a heteroaryl ring having the formula (II)
- R 7 , R 8 , R 9 , and R 10 are independently selected from hydrogen or an alkyl group having 1 to 4 carbon atoms.
- R ; , R 8 , R 9 , and R i0 are independently selected from hydrogen or methyl.
- R ; , R 9 , and R !0 are hydrogen, and R 8 is methyl.
- the compound having the formula (I) is selected from l-methyl-3-(3-(trimetlioxysilyl)propyl)-lH-imidazol-3-ium or N,N,N- trimethyl-3-(irfmethoxysiIyl)propan-i-arnmvu.m.
- the metal oxide support is SiCfr.
- this invention relates to a use of the catalyst system of the invention for producing cyclic carbonates from C0 2 and epoxide- based com pounds .
- the present invention rela tes to a method for preparation of a catalyst system of this invention comprising steps of: (a) refluxing silane compound having formula (ill) with an amine-based compound in an organic solvent at a temperature of 100 to 150 °C for 12 to 72 hours, wherein the mole ratio between the silane compound and amine-based compound is in the range of 5: 1 to 1 :5 to obtain compound (1);
- n represents an integer from 1 to 4.
- R u , R 12 , and R 53 are independently selected from an alkyl group having carbon atoms 1 to 4 or an aikoxy group having 1 to 4 carbon atoms.
- step (b) refluxing the mixture containing the compound (I) obtained from step (a) in an organic solvent and the metal oxide support, selected from MgO, SiCb, ZnO, AI2O3 ,, or TK) 3 ⁇ 4 suspended in the organic solvent at a temperature in the range of about 100 to 200 °C for about 5 to 50 hours, wherein the concentration of compound (I) is in the range of about 5 to 15 % v/v and the concentration of metal oxide is in the range of abou 10 to 20 % w/v; and
- step (c) contacting the pre-catalyst with the metal oxide obtained from step (b) for about 1 to 5 hours, wherein the concentration of the pre-catalyst is in the range of about 1 to 10 % by weight of the metal oxide.
- A is selected from chloride, bromide, or iodide.
- n is 1.
- R n , R 12 , and R 13 are independently selected from an aikoxy group having carbon atoms 1 to 4.
- R ! i , R 12 , and R B are methoxy.
- the amine-based compound is an imidazole- based compound .
- the amine-based compound is N ⁇ rnethylimidazo!e.
- the mole ratio between the silane compound and the amine-based compound is in the range of about 2:1 to 1 :2.
- the organic solvent is an aromatic hydrocarbon solvent.
- the organic solvent is toluene.
- the metal oxide support is Si0 2 .
- contacting the pre-catalyst with the metal oxide obtained from step (b) may be performed by, for example, a dipping method, an impregnation method, a solid state reaction method, or the like, and among them, a solid state reaction method, such as grinding, mulling, or ball milling techniques is preferred because the operation is simple and offers excellent productivity.
- the present invention provides a method for prepara tion of a catalyst system according to the present invention comprising steps of:
- step (b) mixing the product obtained from step (a) with an alkyl halide in an organic solvent at a temperature in the range of about 100 to 150 °C for about. 12 to 72 hours, wherein the mole ratio between the amine-based compound and the alkyl halide is in the range of about 5: 1 to 1 :5; and (c) contacting the pre-catalyst with the metal oxide obtained from step (b) for about 1 to 5 hours, wherein the concentration of the pre-catalyst is in the range of about 1 to 10 % by weight of the metal oxide.
- the amine-based compound has the formula
- R 34 , R 15 , and R !6 are independently selected from an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms;
- R i7 and R iS are independently selected from an alkyl group having I to 4 carbon atoms or an aryl group, or R17 and Ri 8 may be taken together to form a heteroaryl ring.
- q is 1.
- R 14 , R i;> , and R !6 are independently selected from an alkoxy group having 1 to 4 carbon atoms.
- R 14 , R 15 , and R 36 are methoxy.
- R 37 and R 18 are independently selected from an alkyl group having 1 to 4 carbon atoms.
- R 37 is methyl
- R 38 is methyl
- organic solvent is selected from an aromatic hydrocarbon solvent.
- the organic solvent is toluene.
- the metal oxide support is Si0 2 .
- contacting the pre-catalyst with the metal oxide obtained from step (b) may be prepared by, for example, a dipping method, an impregnation method, a solid state reaction method, or the like, and among them, a solid state reaction method, such as grinding, mulling, or ball milling techniques is preferred because the operation is simple and offers excellent productivity.
- the present invention provides a method for producing cyclic carbonates from the reaction of carbon dioxide and epoxide-based compounds comprising reacting epoxide-based compounds with carbon dioxide in the presence of a catalyst system having: a pre-catalyst selected from the compound having the formula BiX z ; a compound having the formula (I); and
- X and Y each independently represent halide
- Rh Ry and R 5 are independently selected from an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms;
- R 4 , R 5 , and R 6 are independently selected from an alkyl group having 1 to 4 carbon atoms or an aryl group, or R 4 , R% and R 6 are taken together to form a heteroaryl ring; and a metal oxide support selected from MgO, SiCb, ZnO, AI2O3 , or TiO: wherein said method is performed using a concentration of the catalyst system that is in the range of 0.1 to 20 mol% relative to the epoxide-based compounds; at a pressure of carbo dioxide in the range of 1 to 100 bar; a temperature in the range of 10 to 200 °C; and a reaction time in the range of 1 to 8 hours.
- the concentration of the catalyst system is in the range of about 0.5 to 10 moI% relative to the epoxide-based compounds.
- the pressure of carbon dioxide is in the range of about 1 to 10 bar.
- the temperature is in the range of about 60 to 120 °C.
- reaction time is in a range of about 2 to 4 hours.
- X is chloride.
- pre-catalyst is B1CI3.
- Y is selected from chloride, bromide, or iodide.
- n 1
- R 1 , R 2 , and R 3 are independently selected from an alkoxy group having I to 4 carbon atoms.
- R ! , R 2 , and R 3 are methoxy.
- R 4 , R 3 , and R 6 are independently selected from an alkyl group having 1 to 4 carbon atoms.
- R 4 , R 5 , and R 6 are methyl.
- R 4 , and R 6 are taken together to form a heteroaryl ring having the formula (II)
- R 7 , R 8 , R 9 , and R i0 are independently selected from hydrogen or an alkyl group having 1 to 4 carbon atoms.
- R 7 , R s , R 9 , and R 10 are independently selected from hydrogen or methyl.
- R 7 , R 9 , and R 10 are hydrogen, and R 8 is methyl.
- the compound having the formula (I) is selected from l-methyl-3-(3-(trimethoxysil ⁇ d)propyl)-lH-imidazol-3-iutn or L r .N,N- trimethyl - 3 ⁇ (trimethoxysily l)propan- 1 - aminium .
- the metal oxide support is Si0 2 .
- a mixture of ALMethylimidazole (about 5 mL) and (3 ⁇ iodopropyl) trimethoxysilane (about 1 1.65 mL) in dry toluene was refluxed for about 48 hours in an inert atmosphere.
- the obtained mixture was washed with diethyl ether several times, and dried under vacuum for about 24 hours.
- the resulting A r ⁇ 3 ⁇ (3-trimethoxysilylpropyI) ⁇ 3- methyl imidazoliom iodide was a brown viscous liquid.
- the structure of the product was identified by 'B-NMR. in DMSO-db as shown in Figure. 2. Functionalization of with ionic liquid
- S1O2 was functionalized with 1 -methyi-3-(3-(trimethoxysilyl)propyi)-l H- imidazoi-3-ium iodide.
- Silica about 4 g was suspended in toluene (about 25 mL.) N- 3- (3-trimethoxysilylpropyl)--3-methyl imidazolium iodide (about 2.5 mL) dissolved in toluene was then added. After stirring the mixture for about 48 hours at about 110 ° €, the silica was allowed to settle down. The supernatant solution was separated by centrifugation and the modified silica was washed with toluene several times prior to being dried for about 24 hours in vacuum.
- Si0 2 was functionalized with Av/V,;V-trimethyl-3- (trimethoxysilyl)propan-l-aniinium iodide followed by quate narization of the amine with methyl iodide.
- Si0 2 (about 4 g) was suspended in toluene (about 25 mL).
- the supernatant solution was separated by centrifugation and the modified silica was washed with toluene several times prior to being dried for about 24 hours in a vacuum.
- the resultant functionalized silica was further reacted with methyl iodide in DMF in the dark for about 2 hours to obtain quaternary ammonium salt. This step was repeated twice to ensure the formation of quatemarized amine.
- the supernatant solution was separated by centrifugation and the modified silica was washed with toluene several times prior to being dried for about 24 hours in vacuum.
- Pre-catalyst loading on the modified Si0 2 The loading of the pre-catalyst was carried out in the glove box. Abo ut 5 wl% and
- the catalysts of the present invention (about 0.5 to lg) and propylene oxide (about 5 mL, 71.4 mmol) were added to the autoclave equipped with a magnetic stir bar.
- the reactions were initialized with addition of 1.0 bar C0 2 (CO2 at a concentration of about 50% and about 100% were used).
- the autoclave was set in an oil- bath at about 60 °C and about 80 °C and stirred at about 500 rpm. After about 3 hours, the vessel was allowed to cool to room temperature in a water bath.
- the crude reaction mixture sample was collected for ⁇ NMR.
- the reaction mixture was filtered, and unreacted propylene oxide was evaporated by a rotary evaporator.
- the propylene carbonate obtained from the reaction was identified by 1H-NMR in CDCI3 ( Figure 4).
- Tire data in Table 2 showed that increasing the temperature from about 80 °C to about 120 °C for Si-NMe 2 -MeI-BiCl3 led to an increase of yield, however, the conversions of CO2 between at about 80 °C and at about 100 to 120 °C were not much different.
- the 0 pressure caused a small effect on the catalytic performance as the data in Table 2 showed that nearly complete conversion of CO2 could be obtained even at about 5 bar C0 2 pressure.
- Table 4 Entry 5 showed that at about 60 °C and about 7 bar CO? pressure were the mildest condition to achieve C0 2 conversion with a high yield (93%).
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Polyesters Or Polycarbonates (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention provides a catalyst system for producing cyclic carbonates comprising: a pre-catalyst selected from the compound having formula B1XZ; a compound having formula (I) wherein: X and Y each independently represent halide; Z represents an integer from 1 to 3; m represents an integer from 1 to 4; R1, R2, and R3 are independently selected from an alkyl group having 1 to 4 carbon atoms or an allcoxy group having 1 to 4 carbon atoms; R4, R3, and R6 are independently selected.from an alkyl group having 1 to 4 carbon atoms or an aryl group, or R4 to R6 are taken together to form a heteroaryl ring; and a metal oxide support selected from MgO, S1O2, ZnO, AI2O3, or TiO2.
Description
CATALYST SYSTEM FOR PRODUCING CYCLIC CARBONATES AND
METHOD RELATED THERETO
FIELD OF INVENTION
This invention relates to a catalyst system for producing cyclic carbonates and a method for preparation of the cyclic carbonates by using the catalyst system.
BACKGROUND OF INVENTION
Carbon dioxide (CO?) emissions, such as from industrial processes and fuel combustion, are becoming a serious problem worldwide because such emissions are considered a primary driver of climate change. According to the Global Energy & C02 Status Report 2017 launched by the International Energy Agency (TEA), global energy- related C02 emissions reached a historic high of 32.5 gigatonnes. Legislators around the globe have started to set limitations on the unrestricted release of CO2 in the atmosphere. Among approaches to solve the problem, the chemical transformation of CO2 into high value chemicals has attracted considerable attention in recent years. Cyclic carbonates are one of those because they can be easily produced from the cycloaddition of CO? to epoxides under mild conditions. Cyclic carbonates are at the center of a multibillion USD market that involves polycarbonates, glycols, and polyesters. However, CO2 is Idnetically and thermodynamically stable, thus it requires a large amount of energy to transform CO? into other chemicals, including cyclic carbonates. As such, a promising approach is to develop effective catalysts that allow for higher conversion of CO at lower temperatures.
Cyclic carbonates are produced from CO? by cycloaddition reaction to epoxides. Several catalyst systems exist to carry out such reaction, however, very few of such systems are capable of operating using impure CO2 under ambient or moderate pressure (0.1-1 MPa). The ability to capture CO2 from gas mixtures is advantageous as it can be easily applied with flue gas and is therefore commercially attractive for cyclic carbonate production. Examples of said catalysts include a bimetallic aluminum (salen) complex disclosed in Energy Environ. Sci., 2010,3, 212-215 which is used for cyclic carbonate production with CO2 having moisture and NOx as impurities in CO . However, said complex has a very high molecular weight and its preparation involves several synthetic
steps because of the elaborated structure of organic framework-coordinating aluminum atoms.
US 9,586.926 B2 disclosed a method for producing cyclic carbonate from carbonation of epoxide by CO . The method is performed via a homogeneous catalyst system comprising a pre-catalyst selected from YCb, Y2O3, Y(N03)3> ScCk or La(¾ and a co-catalyst selected from tefrabutylammonium bromide, 4-dimethylaminopyridine, or bis(triphenylphosphine) iminiirm chloride at a mole ratio in the range of 1 :1 to 1 :2. However, the catalytic activity of this system with impure or diluted CO2 is relatively low under ambient conditions.
Monteiro, et. al. (Applied Catalysis A: General (2017), 544 (25), 46-54) disclosed a catalyst system comprising l~meihyl-3-(3-tiimethoxysilylpiOpyI) imidazolium chloride ionic liquid catalyst supported on titanate nanotubes (TNT) or nano wires (TNW) as a pre catalyst and ZnBr2 as a co-catalyst for synthesizing cyclic carbonates. Although selectivity of the catalyst to CO2 is high, this catalyst was not applied for the conversion of impure or diluted CO2.
Therefore, there is a need to develop a new generation of catalytic systems to produce cyclic carbonates from CO2, especially by using diluted and/or impure CO sources, under mild conditions with high catalytic activity and high selectivity. Accordingly, the present invention is intended to provide a catalyst system for the conversion of CO? and epoxides to cyclic carbonates under mild conditions using pure and impure CO2 having a high catalytic activity and being cost-effective.
SUMMARY OF THE INVENTION in one embodiment, the present invention provides a catalyst system for producing cyclic carbonates from carbon dioxide (CO?) and epoxide-based compounds comprising: a pre-catalyst selected from the compound having the formula BiXz; a compound having the formula (I)
R? W R* Rs
'X
R3 X M X ¾ Fi4
y P
(D
wherein:
X and Y each independently represent halide:
Z represents an integer from 1 to 3; m represents an integer from 1 to 4;
R!, R2, and R3 are independently selected from an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms;
R4, R5, and R6 are independently selected from an alkyl group having 1 to 4 carbon atoms or an aryl group, or R4, R\ and R6 are taken together to form a heteroaryl ring; and a metal oxide support selected from MgO, SiOy ZnO, ARCR or Ti02.
In another embodiment of the invention, the present invention relates to a method for preparation of a catalyst system comprising steps of:
(a) refluxing silane compound having the formula (III) with amine based compound in an organic so Rent at a temperature in the range of about 100 to 150 °C for about 12 to 72 hours, wherein a mole ratio between silane compound and amine based compound is in the range of about 5 : 1 to about 1 5 to obtain compound
CD;
wherein:
A represents halide; n represents an integer from 1 to 4;
Rn, R12, and Rn are independently selected from an alkyl group having carbon atoms 1 to 4 or an alkoxy group having 1 to 4 carbon atoms.
(b) refluxing the mixture containing the compound (I) obtained from step (a) in an organic solvent and the metal oxide support, selected from MgO, SiCfr, ZnO, AI2O3, or 'PO2, suspended in the organic solvent at a temperature in the range of about 100 to 200 °C for about 5 to 50 hours, wherein the concentration of compound (I) is in the range of about 5 to 15 % v/v and the concentration of metal oxide is in the range of about 10 to 20 % w/v; and
(c) contacting the pre-catalyst with the metal oxide obtained from step (b) for about 1 to 5 hours, wherein a concentration of the pre-catalyst is in the range of about 1 to about 10 % by weight of the metal oxide.
In another embodiment of the invention, the present invention relates to a method for preparation of a catalyst system comprising steps of:
(a) refluxing the mixture of amine-based compound in an organic solvent and the metal oxide support, selected from MgO, Si02, ZnO, AI2O3.. or Ti02, suspended in the organic solvent at a temperature in the range of about 100 to 200 °C for about 5 to 50 hours, wherein the concentration of amine-based compound is in the range of about 5 to 15 % v/v and the concentration of metal oxide is in the ran ge of about 10 to 20 % w/v; and;
(b) mixing the product obtained from step (a) with an alky! halide in an organic solvent at a temperature in the range of about 100 to 150 °C for about 12 to 72 hours, wherein the mole ratio between the amine-based compound and the alkyl halide is in the range of about 5:1 to 1 :5; and
(c) contacting the pre-catalyst with the metal oxide obtained from step (b) for about 1 to 5 hours, wherein the concentration of the pre-catalyst is in the range of about 1 to 10 % by weight of the metal oxide.
In another embodiment of the invention, the present invention relates to a method for producing cyclic carbonates, which comprises reacting epoxide-based compounds with carbon dioxide in the presence of a catalyst system comprising: a pre-catalyst selected from the compound having the formula BiXz; a compound having the formula (I)
where:
X and Y each independently represent halide;
Z represents an integer from 1 to a 3; m represents an integer from 1 to 4;
Rh R2, and R3 are independently selected from an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms:
R4, R5, and R6 are independently selected from an alkyl group having 1 to 4 carbon atoms or an aryl group, or R4, R5. and R6 are taken together to form a heteroaryl ring; and a metal oxide support selected from MgO, Si02, ZnO. AbOs, or Ti02 wherein said method is performed using the concentration of the catalyst system in the range of about 0.1 to 20 mol% relative to the epoxide-based compounds; at a pressure of carbon dioxide in the range of about 1 to 100 bar; a temperature in the range of about 10 to 200 °C; and a reaction time in the range of about 1 to 8 hours.
BRIEF DESCRIPTION OF THE DRAWING
Figure 1. Jil-NMR spectrum of l-methyl-3-(3-(trimetlioxysilyi)propyl)-lH- imidazoi-3-ium bromide.
Figure 2. !1 l-NM R spectrum of l-methyl-3-(3-(trimethoxysilyl)propyl)-l H- irnidazol-3-ium iodide.
Figure 3. FT-1R spectru of 1 -methyl-3-(3-(trimethoxysilyl)propyl)·· 1 H-rmidazol- 3~ium iodide supported on Si02.
Figure 4. lH-NMR spectrum of propylene carbonate obtained from the catalyst according to the present invention.
DEI' AILED DESCRIPTIO OF THE INVENTION
The present i vention provides a catalyst system for producing cyclic carbonates with cost-effectiveness and high catalytic activity for conversion of C02 and epoxide-based compounds to cyclic carbona tes. Also, the present invention provides a method of making the cyclic carbonates by using the catalyst system with mild conditions using pure and impure CO?. Details of the present invention can be elucidated according to the specification as follows.
Technical terms or scientific terms used herein have definitions as understood by those having an ordinary skill in the art, unless stated otherwise.
Equipment, apparatus, methods, or chemicals mentioned here means equipment, apparatus, processes, or chemicals commonly operated or used by those skilled in the art, unless explicitly stated otherwise that they are equipment, apparatus, methods, or chemicals specifically used in this invention.
The use of the singular or plural nouns with the term“comprising’ in the claims or in the specification refers to“one” and also“one or more,”“at least one,” and“one or more than one.”
All compositions and/or processes disclosed and claimed are aimed to include aspects of the invention from actions, operation, modifications, or changing of any parameters without performing significantly different experiments from this invention, and obtaining similar objects with the same utilities and results of the present invention according to persons skilled in the art although without mention of the claims specifically. Therefore, substitution or similar objects to the present invention including minor modifications or changes which can be clearly seen by persons skilled in the art should be considered within the scope, spirit, and concept of the invention as appended claims.
Throughout this application, the term“about” is used to indicate that any value presented herein may potentially vary or deviate. Such variation or deviation may result from errors of apparatus, methods used in calculation, or from individual operator implementing apparatus or methods. These include variations or deviations caused by changes of the physical properties.
Following is a detailed description of the invention without any intention to limit the scope of the invention.
According to one embodiment of the invention, the present invention provides a catalyst system for producing cyclic carbonates comprising: a pre-catalyst selected from the compound having the formula BiX¾ a compound having the formula (I)
wherein:
X and Y each independently represent halide;
Z represents an integer from 1 to 3; m represents an integer from 1 to 4;
R5, R2, and RJ are independently selected from an alkyl group having 1 to 4 carbon atoms or an a!koxy group having 1 to 4 carbon atoms;
R4, R:\ and R6 are independently selected from an alkyl group having 1 to
4 carbon atoms or an aryl group or R4, R5, and R6 are taken together to form a heteroaryl ring; and a metal oxide support selected from MgO, Si02, ZnO, AI2O3, or Ί1O2.
In another exemplary embodiment, X is chloride.
In a preferred exemplary embodiment, the pre-catalyst is BiCR.
In another exemplary embodiment, Y is selected from chloride, bromide, or iodide. in another exemplary embodiment m is 1.
In another exemplary embodiment, R1, R2, and R3 are independently selected from an alkoxy group having 1 to 4 carbon atoms. Preferably, R1, R2, and R3 are methoxy.
In another exemplary embodiment, R4, R3, and R6are independently selected from an alkyl group having 1 to 4 carbon atoms. Preferably, R4, R5, and R6 are methyl.
In another exemplary embodiment R4, R5, and R° are taken together to form a heteroaryl ring having the formula (II)
wherein:
R7, R8, R9, and R10 are independently selected from hydrogen or an alkyl group having 1 to 4 carbon atoms.
In another exemplary embodiment R;, R8, R9, and Ri0 are independently selected from hydrogen or methyl.
In a preferred exemplary embodiment, R;, R9, and R!0 are hydrogen, and R8 is methyl.
In a preferred exemplary' embodiment the compound having the formula (I) is selected from l-methyl-3-(3-(trimetlioxysilyl)propyl)-lH-imidazol-3-ium or N,N,N- trimethyl-3-(irfmethoxysiIyl)propan-i-arnmvu.m.
In a preferred exemplary embodiment, the metal oxide support is SiCfr.
In another embodiment of the invention, this invention relates to a use of the catalyst system of the invention for producing cyclic carbonates from C02 and epoxide- based com pounds .
In another embodiment of the invention, the present invention rela tes to a method for preparation of a catalyst system of this invention comprising steps of:
(a) refluxing silane compound having formula (ill) with an amine-based compound in an organic solvent at a temperature of 100 to 150 °C for 12 to 72 hours, wherein the mole ratio between the silane compound and amine-based compound is in the range of 5: 1 to 1 :5 to obtain compound (1);
wherein:
A represents halide n represents an integer from 1 to 4;
Ru, R12, and R53 are independently selected from an alkyl group having carbon atoms 1 to 4 or an aikoxy group having 1 to 4 carbon atoms.
(b) refluxing the mixture containing the compound (I) obtained from step (a) in an organic solvent and the metal oxide support, selected from MgO, SiCb, ZnO, AI2O3,, or TK)¾ suspended in the organic solvent at a temperature in the range of about 100 to 200 °C for about 5 to 50 hours, wherein the concentration of compound (I) is in the range of about 5 to 15 % v/v and the concentration of metal oxide is in the range of abou 10 to 20 % w/v; and
(c) contacting the pre-catalyst with the metal oxide obtained from step (b) for about 1 to 5 hours, wherein the concentration of the pre-catalyst is in the range of about 1 to 10 % by weight of the metal oxide.
In another exemplary embodiment, A is selected from chloride, bromide, or iodide. In another exemplary embodiment, n is 1.
In another exemplary embodiment, Rn, R12, and R13 are independently selected from an aikoxy group having carbon atoms 1 to 4.
In a preferred exemplary embodiment, R! i, R12, and RB are methoxy.
In another exemplary embodiment, the amine-based compound is an imidazole- based compound .
In a preferre exemplary embodiment, the amine-based compound is N~ rnethylimidazo!e.
In another exemplary embodiment, the mole ratio between the silane compound and the amine-based compound is in the range of about 2:1 to 1 :2.
In another exemplary embodiment, the organic solvent is an aromatic hydrocarbon solvent.
In a preferred exemplary embodiment, the organic solvent is toluene.
In a preferred exemplary embodiment, the metal oxide support is Si02.
In one embodiment, according to step (c), contacting the pre-catalyst with the metal oxide obtained from step (b) may be performed by, for example, a dipping method, an impregnation method, a solid state reaction method, or the like, and among them, a solid state reaction method, such as grinding, mulling, or ball milling techniques is preferred because the operation is simple and offers excellent productivity.
In another embodiment of the invention, the present invention provides a method for prepara tion of a catalyst system according to the present invention comprising steps of:
(a) refluxing the mixture of amine-based compound in an organic solvent and tire metal oxide support, selected from MgO, SiCh, ZnO, AI2O3, or Ti02, suspended in the organic solvent at a temperature in the range of about 100 to 200 °C for about 5 to 50 hours, wherein the concentration of the amine -based compound is in the range of about 5 to 15 % v/v and the concentration of metal oxide is in the range of about 10 to 20 % vv/v; and;
(b) mixing the product obtained from step (a) with an alkyl halide in an organic solvent at a temperature in the range of about 100 to 150 °C for about. 12 to 72 hours, wherein the mole ratio between the amine-based compound and the alkyl halide is in the range of about 5: 1 to 1 :5; and
(c) contacting the pre-catalyst with the metal oxide obtained from step (b) for about 1 to 5 hours, wherein the concentration of the pre-catalyst is in the range of about 1 to 10 % by weight of the metal oxide.
In another exemplary embodiment, the amine-based compound has the formula
(IV).
wherein: q represents an integer from 1 to 4:
R34, R15, and R!6 are independently selected from an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms;
Ri7 and RiS are independently selected from an alkyl group having I to 4 carbon atoms or an aryl group, or R17 and Ri 8 may be taken together to form a heteroaryl ring.
In a preferred exemplary embodiment, q is 1.
In another exemplary embodiment R14, Ri;>, and R!6 are independently selected from an alkoxy group having 1 to 4 carbon atoms. Preferably, R14, R15, and R36 are methoxy.
In another exemplary embodiment, R37 and R18 are independently selected from an alkyl group having 1 to 4 carbon atoms.
In a preferred exemplary embodiment, R37 is methyl.
In a preferred exemplary embodiment, R38 is methyl.
In another exemplary embodiment, wherein the organic solvent is selected from an aromatic hydrocarbon solvent.
In a preferred exemplary embodiment, the organic solvent is toluene.
In a preferred exemplary embodiment, the metal oxide support is Si02.
In one embodiment, according to step (c), contacting the pre-catalyst with the metal oxide obtained from step (b) may be prepared by, for example, a dipping method, an impregnation method, a solid state reaction method, or the like, and among them, a solid state reaction method, such as grinding, mulling, or ball milling techniques is preferred because the operation is simple and offers excellent productivity.
In another embodiment of the invention, the present invention provides a method for producing cyclic carbonates from the reaction of carbon dioxide and epoxide-based compounds comprising reacting epoxide-based compounds with carbon dioxide in the presence of a catalyst system having: a pre-catalyst selected from the compound having the formula BiXz; a compound having the formula (I); and
where:
X and Y each independently represent halide;
Z represents an integer from 1 to a 3; m represents an integer from 1 to 4;
Rh Ry and R5 are independently selected from an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms;
R4, R5, and R6 are independently selected from an alkyl group having 1 to 4 carbon atoms or an aryl group, or R4, R% and R6 are taken together to form a heteroaryl ring; and a metal oxide support selected from MgO, SiCb, ZnO, AI2O3, or TiO:
wherein said method is performed using a concentration of the catalyst system that is in the range of 0.1 to 20 mol% relative to the epoxide-based compounds; at a pressure of carbo dioxide in the range of 1 to 100 bar; a temperature in the range of 10 to 200 °C; and a reaction time in the range of 1 to 8 hours. In a preferred exemplary embodiment, the concentration of the catalyst system is in the range of about 0.5 to 10 moI% relative to the epoxide-based compounds.
In a preferred exemplary embodiment, the pressure of carbon dioxide is in the range of about 1 to 10 bar.
In a preferred exemplary embodiment, the temperature is in the range of about 60 to 120 °C.
In a preferred exemplary embodiment, the reaction time is in a range of about 2 to 4 hours. in another exemplary embodiment, X is chloride. in a preferred exemplary embodiment, the pre-catalyst is B1CI3. In another exemplary embodiment, Y is selected from chloride, bromide, or iodide.
In another exemplary embodiment, m is 1.
In another exemplary embodiment, R1, R2, and R3 are independently selected from an alkoxy group having I to 4 carbon atoms. Preferably, R!, R2, and R3 are methoxy.
In another exemplary embodiment, R4, R3, and R6 are independently selected from an alkyl group having 1 to 4 carbon atoms. Preferably, R4, R5, and R6 are methyl.
In another exemplary embodiment, R4,
and R6 are taken together to form a heteroaryl ring having the formula (II)
1.4 where:
R7, R8, R9, and Ri0 are independently selected from hydrogen or an alkyl group having 1 to 4 carbon atoms.
In another exemplary embodiment, R7, Rs, R9, and R10 are independently selected from hydrogen or methyl.
In a preferred exemplary embodiment, R7, R9, and R10 are hydrogen, and R8 is methyl.
In a preferred exemplary embodiment, the compound having the formula (I) is selected from l-methyl-3-(3-(trimethoxysil}d)propyl)-lH-imidazol-3-iutn or L r.N,N- trimethyl - 3 · (trimethoxysily l)propan- 1 - aminium .
In a preferred exemplary embodiment, the metal oxide support is Si02.
Hereafter, examples of the invention are· shown without any purpose to limit any scope of the invention.
Example
Chemicals and consumables
All chemicals were purchased from commercial sources and used as received. Early transition metal halides were stored and handled inside a g!ovebox. Metal-free compounds were stored in chemical cabinets and used without further precautions. Silica supports used for the preparation of the heterogeneous bismuth catalyst were thermally treated at about 150 °C in an oven before use to remove traces of moisture. Pure and diluted COi (CO2 at a concentration of 50% in air) were received in metal cylinders and dosed via regulator.
Synthesis of l-methyl-3-f3-ftrimethoxysilyl)propyl)-lH-imidazol-3-ium bromide
Toluene, reflux
W- meShyiimi iizoie
(3 - bro o p ropy I )tri met h oxy si I a ne
imklazo!-S-ium bromide
The mixture of /V-Methylimidazole (about 5 mL) and (3 -bro o propyl) trimethoxysilane (about 1 1.65 mL) in dry toluene was refluxed for about 48 hours in an inert atmosphere. The obtained mixture was washed with diethyl ether several times, and dried under a vacuum for about 24 hours. The resulting A;--3-(3- trimethoxysilylpropyl)-3·· methyl imidazolium bromide was a brownish viscous liquid. The structure of the product was identified by ftTNMR in DMSO-dd as shown in Figure 1.
Synthesis of l-methyl-3-f3- propvl)-lH-imidazol-3-ium iodide
To uene, reflux
N-methyiimidazote 1-methyl-3-(3-
(3--iocioi>ropyi}fd ethoxysiiane
{trimethoxysifyi)propyif 1 imidazol-3~ium iodide
A mixture of ALMethylimidazole (about 5 mL) and (3~iodopropyl) trimethoxysilane (about 1 1.65 mL) in dry toluene was refluxed for about 48 hours in an inert atmosphere. The obtained mixture was washed with diethyl ether several times, and dried under vacuum for about 24 hours. The resulting Ar~3~(3-trimethoxysilylpropyI)~3- methyl imidazoliom iodide was a brown viscous liquid. The structure of the product was identified by 'B-NMR. in DMSO-db as shown in Figure. 2. Functionalization of with ionic liquid
3-fum iodide
S1O2 was functionalized with 1 -methyi-3-(3-(trimethoxysilyl)propyi)-l H- imidazoi-3-ium iodide. Silica (about 4 g) was suspended in toluene (about 25 mL.) N- 3- (3-trimethoxysilylpropyl)--3-methyl imidazolium iodide (about 2.5 mL) dissolved in toluene was then added. After stirring the mixture for about 48 hours at about 110 °€, the silica was allowed to settle down. The supernatant solution was separated by centrifugation and the modified silica was washed with toluene several times prior to being dried for about 24 hours in vacuum.
The FT-IR spectrum of the prepared catalyst (Figure 3) showed several signals corresponding to the presence of organic species with aromatic character on the surface as seen from the signals in the 2890 to 3151 cm ! region and in the 1450 to 1630 cm 1 region. The presence of organic species loaded on the support was identified by the following elemental analysis: C (14.05%); H (2.65%); N (3.83%).
Additionally, Si02 was functionalized with Av/V,;V-trimethyl-3- (trimethoxysilyl)propan-l-aniinium iodide followed by quate narization of the amine with methyl iodide. Si02 (about 4 g) was suspended in toluene (about 25 mL). iV~3~(3~ trimethoxysilyipropyl)-3-dimethylamme (about 2.5 ml.) dissolved in toluene was then added. After stirring the mixture for about 48 hours at about 110 °C, the silica was allowed to settle down. The supernatant solution was separated by centrifugation and the modified silica was washed with toluene several times prior to being dried for about 24 hours in a vacuum. The resultant functionalized silica was further reacted with methyl iodide in DMF in the dark for about 2 hours to obtain quaternary ammonium salt. This step was repeated twice to ensure the formation of quatemarized amine. The supernatant solution was separated by centrifugation and the modified silica was washed with toluene several times prior to being dried for about 24 hours in vacuum.
Pre-catalyst loading on the modified Si02 The loading of the pre-catalyst was carried out in the glove box. Abo ut 5 wl% and
10 wt% of metal of pre-catalyst with respect to the weight of silica was loaded on the functionalized supports. Bids, as a pre-catalyst, was ground with the support through a manual mechanical grinding process. The mixture of modified silica support and pre- catalyst was ground for about 2 hours in the glove box and used as such. Synthesis of cyclic carbonates using autoclave with pure and diluted C02
Cyclic carbonates were synthesized using the catalysts of the present invention to test their catalytic activity. The synthesis was carried out in a 75 ml.· autoclave under inert atmosphere (glove box). The catalysts of the present invention (about 0.5 to lg) and propylene oxide (about 5 mL, 71.4 mmol) were added to the autoclave equipped with a magnetic stir bar. The reactions were initialized with addition of 1.0 bar C02 (CO2 at a concentration of about 50% and about 100% were used). The autoclave was set in an oil- bath at about 60 °C and about 80 °C and stirred at about 500 rpm. After about 3 hours, the vessel was allowed to cool to room temperature in a water bath. The crude reaction mixture sample was collected for Ή NMR. For isolation of pure propylene carbonate, the reaction mixture was filtered, and unreacted propylene oxide was evaporated by a rotary evaporator. The propylene carbonate obtained from the reaction was identified by 1H-NMR in CDCI3 (Figure 4).
From Table I, the initial studies on heterogeneous catalysts were carried out at about 60 and 80 °C and 10 bar CO? pressure using either pure CO or diluted C02 at a concentration of about 50%. The studie catalysts were AC/vOY-trimethyl-3- (trimethoxysilyl)propan-l~aminium iodide and B1CI3 supported on Si02 (SiNMe2~MeI- BiCb), and l-rnethyl-3~(3~(frimethoxysily])propyl)-lH~imidazol~3-ium iodide and BiCh supported on Si02 (Si-Iml-BiCh). Before running catalytic activity tests with the metal containing catalysts, the catalytic efficiency of the metal-free functionalized supports (entries 1 to 4) were studied. Of note, the metal-free functionalized supports showed a moderate to good catalytic activity in the cycloaddition of CO2 to propylene oxide. However, this catalytic activity in all entries was improved by the presence of BiCl3. The catalytic activit in the presence of metal was improved about 10 to 20% compared to the absence of metal. A comparison between entries 5 and 6 suggested that the metal loading could be reduced to about 5% by weight without a minimal difference in catalytic activity. The reaction condition at about 80 °C and about 10 bar using pure C02 with 10% metal loading of SiNMez-Mel-BiCh (entry 9) provided the highest reaction yields with a completion of CO2 conversion In about 3 hours. Reducing the temperature to about 60 °C, with pure or diluted CO2 (concentration of about 50%) led to slightly lower conversion. Using the diluted CO2 led to a decrease of the reaction yield when operating at about 80 °C, however, at. about 60 °C, the yields of the reactions using pure CO2 and the diluted C02 were similar. SiNMe2-MeTBiC]3 was recovered after the catalytic run and reused for two additional consecutive cycles. The results showed that the catalyst was recyclable with a
progressive loss of catalytic activity. This might probably be due to the exposition of the catalyst to air and/or to losses of material occurring when recycling the catalyst.
Table 1 Catalytic activity of the catalyst.
According to the good catalytic activity of SiNMe-r-Mel-BiCh and Si-Imi-BiCly 5 further studies and optimization by varying temperature and pressure using the diluted C02 (concentration of about 50%) were carried out as shown in Table 2.
Tire data in Table 2 showed that increasing the temperature from about 80 °C to about 120 °C for Si-NMe2-MeI-BiCl3 led to an increase of yield, however, the conversions of CO2 between at about 80 °C and at about 100 to 120 °C were not much different. The 0 pressure caused a small effect on the catalytic performance as the data in Table 2 showed that nearly complete conversion of CO2 could be obtained even at about 5 bar C02 pressure.
Table 4 (Entry 5) showed that at about 60 °C and about 7 bar CO? pressure were the mildest condition to achieve C02 conversion with a high yield (93%). When using Si-Iml-BiCb, the most interesting observation was that CO2 conversion did not generally increase with the temperature, but generally decreased, especially when the temperature rose from about 100 to 120 °C. This might be because the vaporization of propylene oxide while increasing temperature could reduce the contact between the substrate and the catalyst. This observation was supported by the fact that the conversion decreased when the temperature increased from about 100 to 120 °C at the CO pressure of about 5 bar (Table 2, Entries 23 and 24), since this condition favored propylene oxide evaporation. Table 2 Catalytic activity of the prepared catalyst system under several reaction conditions.
As a person skilled in the art will readily appreciate, the above description is meant as an illustration of implementation of the principles this invention. This description is not intended to limit the scope or application of this invention in that the invention is susceptible to modification, variation, and change, without departing from the spirit of this invention, as defined in the following claims.
BEST MODE OF THE INVENTION
Best mode of the invention is as provided in the description of the invention.
Claims
1 . A catalyst system for producing cyclic carbonates comprising: a pre-catalyst selected from the compound having formula BiXz; a compound having formula (I)
CO wherein:
X and Y each independently represent halide:
Z represents an integer from 1 to 3; m represents an integer fro 1 to 4;
Rh R2, and R:i are independently selected from an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms;
If’. R5, and R6 are independently selected from an alkyl group having 1 to 4 carbon atoms or an aryl group, or R4, R5, and R6 are taken together to form a heteroaryl ring; and a metal oxide support selected from MgO, SiCb, ZnO, AI2O3. or TiCb.
2. The catalyst system according to claim 1 , wherein X is chloride.
3. The catalyst system according to claim 1 , wherein the pre catalyst is BiCfr.
4. The catalyst system according to claim 1, wherein Y is selected from chloride, bromide, or iodide.
5. The catalyst system according to claim 1 , wherein m is 1.
6. The catalyst system according to claim .1 , wherein R1, Rz, and R3 are independently selected from an alkoxy group having 1 to 4 carbon atoms.
7. The catalyst system according to claim 6, wherein R1 is methoxy.
8. The catalyst system according to claim 6, wherein R.2, is methoxy.
9. The catalyst system according to claim 6, wherein R3 is methoxy.
10. The catalyst system according to claim 1, wherein R1, R5, and R6 are independently selected from an alkyl group having 1 to 4 carbon atoms.
1 1. The catalyst system according to claim 10. wherein R4 is methyl.
12. The catalyst system according to claim 10. wherein R3 is methyl.
13. The catalyst system according to claim 10, wherein R6 is methyl.
14. The catalyst system according to claim 1 , wherein RT R3, and R6 are taken together to form a heteroaryl ring having formula (II)
where R1, R8, R9, and R10 are independently selected from hydrogen or an alkyl group having 1 to 4 carbon atoms.
15. The catalyst system according to claim 14, wherein R7. R8, R9, and R10 are independently selected from hydrogen or methyl.
16. The catalyst system according to claim 15, wherein R7 is hydrogen.
The catalyst system according to claim 15, wherein R8 is methyl
18. The catalyst system according to claim 15, wherein R9 is hydrogen.
19. The catalyst system according to claim 15, wherein Ri<J is hydrogen.
20. The catalyst system according to claim 1, wherein the compound having formula (I) is selected from l~metliyl-3-(3~(trimethoxysilyl)propyl)-lH~imidazol~3-ium or /V.ATV--triniethyl-3~(trimethoxysi]yI)propan- 1 -aminium.
21. The catalyst system according to claim 1, wherein the metal oxide support is SiCk.
22. A use of the catalyst system for producing cyclic carbonates, the catalyst system comprising: a pre-catalyst selected from the compound having formula BiXz; a compound having formula (I)
wherein;
X and Y each independently represent halide;
Z represents an integer from 1 to 3; rn represents an integer from 1 to 4;
R1, R2, and R3 are independently selected from an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms;
R4, R5, and R6 are independently selected from an alkyl group having 1 to 4 carbon atoms or an aryl group, or R4, R\ and R6 are taken together to form a heteroaryl ring; and a metal oxide support selected from MgO, SiCfr, ZnO, AkCfr, or TiCfr.
23. The use of the catalyst system according to claim 22, wherein X is chloride.
24. The use of the catalyst system according to claim 22, wherein the pre catalyst is BiCl3.
25. The use of the catalyst system according to claim 22, wherein Y is selected from chloride, bromide, or iodide.
26. The use of the catalyst system according to claim 22, wherein m is 1.
27. The use of the catalyst system according to claim 22, wherein R1, R2, and R3 are independently selected from an alkoxy group having 1 to 4 carbon atoms.
28. The use of the catalyst system according to claim 27, wherein R1 is methoxy.
29. The use of the catalyst system according to claim 27, wherein R2, is methoxy.
30. The use of the catalyst system according to claim 27, wherein R3 is methoxy.
31. The use of the catalyst system according to claim 22, wherein R4, R’, and R6 are independently selected from an alkyl group having 1 to 4 carbon atoms.
32. The use of the catalyst system according to claim 31 , wherein R4 is methyl.
33. The use of the catalyst system according to claim 31 , wherein R5 is methyl.
34. The use of the catalyst system according to claim 31, wherein R6 is methyl.
35. The use of the catalyst system according to claim 22, wherein R4, R\ and R6 arc taken together to form a heteroaryl ring having formula (II)
where R7, R8, R9, and R10 are independently selected from hydrogen or an alkyl group having 1 to 4 carbon atoms.
36. The use of the catalyst system according to claim 35, wherein R?, Rs, R9, and R10 are independently selected from hydrogen or methyl.
37. The use of the catalyst system according to claim 36, wherein R7 is hydrogen.
38. The use of the catalyst system according to claim 36, wherein Rs is methyl.
39. The use of the catalyst system according to claim 36, wherein R9 is hydrogen.
40. The use of the catalyst system according to claim 36, wherein R10 is hydrogen.
41. The use of the catalyst system according to claim 22, wherein the compound having formula (I) is selected from l-me†hyl-3-(3-(tiimetlioxysilyI)propyl) iH~imidazol-3- ium or ./V,/Y,At-iTiinethyl-3 -(trimethoxysil llpropan- 1 -arnini am.
42. The use of the catalyst system according to claim 22, wherein the metal oxide support is SiCb.
43. A method for preparation of a catalyst system for producing cyclic carbonates comprising steps of:
(a) refluxing a silane compound having formula (III) with an amine-based compound in an organic solvent at a temperature of 100 to 150 °C for 12 to 72 hours, wherein the mole ratio between the silane compound and the amine-based compound is in the range of 5:1 to 1 5 to obtain compound (I);
wherein:
A represents halide; n represents an integer from 1 to 4;
Rn, R12, and R13 are independently selected from an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms.
(b) refluxing the mixture containing the compound (I) obtained from step (a) in an organic solvent and the metal oxide support, selected from MgO, SiCfr, ZnO, AfrOy or TiCfr, suspended in the organic solvent at a temperature in the range of 100 to
200 °C for 5 to 50 hours, wherein the concentration of compound (I) is in the range of 5 to 15 % v/v and the concentration of metal oxide is in the range of 10 to 20 % w/v; and
(c) contacting the pre-catalyst with the metal oxide obtained from step (b) for 1 to 5 hours, wherein the concentration of the pre-catalyst is in the range of 1 to 10 % by weight of the metal oxide.
44. The method according to claim 43, wherein A is selected from chloride, bromide, or .iodide.
45. The method according to claim 43, wherein n is 1.
46. The method according to claim 43, wherein Ru, R12, and R13 are independently selected from an alkoxy group having 1 to 4 carbon atoms.
47. The ethod according to claim 46, wherein R11 is methoxy.
48. The method according to claim 46, wherein Rl2 is methoxy.
49. The method according to claim 46, wherein R13 is methoxy.
50. The method according to claim 43, wherein the amine-based compound is an imidazole-based compound.
51. The method according to claim 50, wherein the amine-based compound is N- methylimiclazole.
52. The method according to claim 43, wherein the mole ratio between the silane compound and amine-based compound is in the range of 2:1 to 1 :2.
53. The method according to claim 43, wherein the organic solvent is an aromatic hydrocarbon solvent.
54. The method according to claim 53 wherein the organic solvent is toluene.
55. The method according to claim 43, wherein the metal oxide support is SiO?.
56. The method according to claim 43, wherein step (c) is performed using a dipping method, an impregnation method, or a solid state reaction method.
57. A method for preparation of a catalyst system for producing cyclic carbonates co prising steps of:
(a) refluxing the mixture of the amine-based compound in an organic solvent and the metal oxide support, selected from MgO, SiO , ZnO, A1203 or TiCb, suspended in the organic solvent at i 00 to 200 °C for 5 to 50 hours, wherein the concentration
of the amine -based compound is in the range of 5 to 15 % v/v and the concentration of metal oxide is in the range of 10 to 20 % w/v; and;
(b) mixing the product obtained from step (a) with an alkyl halide in an organic solvent at a temperature of 100 to 150 °C for 12 to 72 hours wherein the mole ratio between the amine -based compound and the alkyl halide is in the range of 5: 1 to 1 :5; and
(c) contacting the pre-catalyst with the metal oxide obtained from step (b) for 1 to 5 hours, wherein the concentration of the pre-catalyst is in the range of 1 to 10 % by weight of the metal oxide.
58. The method according to claim 57, wherein the amine-based compound has formula
(åV).
wherein q represents an integer from 1 to 4;
R14, Ri ;>, and Ri6 are independently selected from an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms;
R 7 and R18 are independently selected from an alkyl group having 1 to 4 carbon atoms or an aryl group, or Rl / and R18 may be taken together to form a heteroaryi ring.
59. The method according to claim 57, wherein q is 1.
60. The method according to claim 59, wherein R14, Ri3, and Ri6 are independently selected from an alkoxy group having ! to 4 carbon atoms.
61. The method according to claim 60, wherein R14 is methoxy.
62. The method according to claim 60, wherein R15 is methoxy.
63. The method according to claim 60, wherein Ri6 is methoxy.
64. The method according to claim 57, wherein R17 and R18 are independently selected from an alkyl group having 1 to 4 carbon atoms.
65. The method according to claim 64, wherein R! 1 is methyl.
66. The method according to claim 64, wherein R!8 is methyl.
67. The method according to claim 57, wherein the organic solvent is selected from an aromatic hydrocarbon solvent.
68. The method according to claim 67 wherein the organic solvent is toluene.
69. The method according to claim 57, wherein the metal oxide support is S1O2.
70. The method according to claim 57, wherein step (c) is performed using a dipping method, an impregnation method, or a solid state reaction method.
71. A method for producing cyclic carbonates from the reaction of carbon dioxide and epoxide-based compounds which comprises reacting epoxide-based compounds with carbon dioxide in the presence of a catalyst system comprising: a pre-catalyst selected from the compound having formula BiXz; a compound having formula (I); and
a metal oxide support selected from MgO, Si02, ZnO, AI2O3, or T1O2 where:
X and Y each independently represent halide;
Z represents an integer from 1 to a 3; m represents an integer from 1 to 4;
RA R2, and R3 are independently selected from an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms;
R4, R5, and R6 are independently selected from an alkyl group having 1 to 4 carbon atoms or an aryl group, or R4, R\ and R6 axe taken together to form a heteroaryl ring. wherein said method is performed using a concentration of the catalyst system in the range of 0.1 to 20 moi% relative to the epoxide-based compounds; at a pressure of carbon dioxide in the range of 1 to 100 bar-; a temperature in the range of 10 to 200 °C; and a reaction time in the range of 1-8 hours.
72. The method according to claim 71, wherein the concentration of the catalyst system is in the range of 0.5 to 10 mol% relative to the epoxide-based compounds.
73. The method according to claim 71, wherein the pressure of carbon dioxide is in the. range of 1 to 10 bar.
74. The method according to claim 71, wherein the temperature is in the range of 60 to 120 °C.
75. The method according to claim 71 , wherein the reaction time is in the range of 2 to 4 hours.
76. The method according to claim 71, wherein X is chloride·.
77. The method according to claim 71, wherein the pre catalyst is Bids.
78. The method according to claim 71 , wherein Y is selected from chloride, bromide, or iodide.
79. The method according to claim 71, wherein m is 1.
80. The method according to claim 71 , wherein R5, R2, and R3 are independently selected from an alkoxy group having 1 to 4 carbon atoms.
81. The method according to claim 80, wherein R1 is methoxy.
82. The method according to claim 80, wherein R2 is methoxy.
83. The method according to claim 80, wherein
is methoxy.
84. The method according to claim 71 , wherein R4, R\ and R6 are independently sel ected from an alkyl group having 1 to 4 carbon atoms.
85. The method according to claim 84, wherein R'· is methyl.
86. The method according to claim 84, wherein R5 is methyl.
87. The method according to claim 84, wherein R6 is methyl.
88. The method according to claim 71 , wherein R4, R5, and R6 are taken together to form a heteroaryl ring having formula (II)
where R;, R8, R9, and R50 are independently selected from hydrogen or an alkyl group having 1 to 4 carbon atoms.
89. The method according to claim 88, wherein R7, R8, R9, and R10 are independently selected from hydrogen or methyl.
90. The method according to claim 89, wherein R7 is hydrogen.
91. The method according to claim 89, wherein R8 is methyl.
92. The method according to claim 89, wherein R9 is hydrogen.
93. The method according to claim 89, wherein Ri0 is hydrogen.
94. The method according to claim 71, wherein the compound having formula (I) is selected from l-meihyl-3-(3-(irhnethoxysilyl)propyl)-lfl--iniidazol-3-ium or NKr,N- trimethyl-3-(trimethoxysilyl)propan-l-amininm.
95. The method according to claim 71, wherein the metal oxide support is Si02.
ROG/TH2b!9/dq00842
WO 2020/060499 PCT/TH2019/000042
m
Figure 2
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US201862732987P | 2018-09-18 | 2018-09-18 | |
| PCT/TH2019/000042 WO2020060499A1 (en) | 2018-09-18 | 2019-09-18 | Catalyst system for producing cyclic carbonates and method related thereto |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| EP3852921A1 true EP3852921A1 (en) | 2021-07-28 |
| EP3852921C0 EP3852921C0 (en) | 2023-06-07 |
| EP3852921B1 EP3852921B1 (en) | 2023-06-07 |
Family
ID=69187883
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP19842423.6A Active EP3852920B1 (en) | 2018-09-18 | 2019-09-18 | Catalyst system for producing cyclic carbonates and method related thereto |
| EP19842424.4A Active EP3852921B1 (en) | 2018-09-18 | 2019-09-18 | Catalyst system for producing cyclic carbonates and method related thereto |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP19842423.6A Active EP3852920B1 (en) | 2018-09-18 | 2019-09-18 | Catalyst system for producing cyclic carbonates and method related thereto |
Country Status (6)
| Country | Link |
|---|---|
| US (2) | US11938467B2 (en) |
| EP (2) | EP3852920B1 (en) |
| JP (2) | JP7500576B2 (en) |
| KR (2) | KR102588583B1 (en) |
| CN (2) | CN113164940B (en) |
| WO (2) | WO2020060498A1 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112495431B (en) * | 2020-11-24 | 2022-02-11 | 中国科学院过程工程研究所 | Method for synthesizing cyclic carbonate by mild catalysis of multi-site ionic liquid |
| CN114917955B (en) * | 2022-06-06 | 2023-11-10 | 辽宁大学 | Nitrogen-containing MOFs material and application thereof in catalysis of low-concentration CO 2 Application in cycloaddition reaction |
| KR20240016885A (en) | 2022-07-29 | 2024-02-06 | 명지대학교 산학협력단 | Catalyst for producing cyclic carbonate from carbon dioxide and method for producing cyclic carbonate using the same |
Family Cites Families (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2773070A (en) * | 1952-10-31 | 1956-12-04 | Jefferson Chem Co Inc | Catalytic process for producing alkylene carbonates |
| CN1189246C (en) * | 2002-11-26 | 2005-02-16 | 大连理工大学 | High activity catalyzer utilized to synthesize cyclic carbonate |
| CN103313940A (en) * | 2010-11-16 | 2013-09-18 | 耶路撒冷希伯来大学伊萨姆研究开发有限公司 | Bismuth oxyhalide compounds useful as photocatalysts |
| WO2012139994A1 (en) * | 2011-04-13 | 2012-10-18 | Basf Se | Process for coupling epoxides and carbon dioxide |
| CN102775378B (en) | 2011-12-20 | 2015-10-28 | 湖南大学 | A kind of solvent-free process for catalytic synthesis of cyclic carbonate |
| CN102838583A (en) | 2012-09-10 | 2012-12-26 | 南昌航空大学 | Method for preparing cyclic carbonate by using functionalized quaternary phosphonium salt ionic liquid |
| CN105377827A (en) | 2013-07-09 | 2016-03-02 | 阿卜杜拉国王科技大学 | Methods of making alkylene carbonates and methods of converting CO2 |
| TWI636980B (en) * | 2013-07-19 | 2018-10-01 | 獨立行政法人產業技術綜合研究所 | Method for producing cyclic carbonate |
| CN103447091B (en) * | 2013-09-05 | 2016-03-30 | 中国科学院长春应用化学研究所 | The method of four tooth pyridine radicals schiff base metal complexes, its preparation method and cyclic carbonate |
| TWI519347B (en) * | 2013-10-24 | 2016-02-01 | 財團法人工業技術研究院 | Catalyst system and method for manufacturing cyclic carbonate by the same |
| BR112016014012B1 (en) * | 2013-12-20 | 2021-01-05 | Saudi Basic Industries Corporation | catalyst system for polymerization of an olefin, comprising a compound, process for preparing said system and uses of the compound |
| CN105080613A (en) * | 2014-05-14 | 2015-11-25 | 中国石油化工股份有限公司 | Catalyst for preparation of ethylene carbonate and preparation method of ethylene carbonate |
| WO2015185489A1 (en) * | 2014-06-02 | 2015-12-10 | Sabic Global Technologies B.V. | Procatalyst for polymerization of olefins |
| JP6765098B2 (en) | 2016-07-14 | 2020-10-07 | 国立研究開発法人産業技術総合研究所 | Magnetic nanoparticles immobilized imidazolium hydrogen carbonate |
| CN106732770B (en) * | 2016-12-02 | 2019-11-08 | 太原理工大学 | In a mild condition by CO2It is converted into the catalyst and method of cyclic carbonate |
-
2019
- 2019-09-18 EP EP19842423.6A patent/EP3852920B1/en active Active
- 2019-09-18 EP EP19842424.4A patent/EP3852921B1/en active Active
- 2019-09-18 JP JP2021539329A patent/JP7500576B2/en active Active
- 2019-09-18 WO PCT/TH2019/000041 patent/WO2020060498A1/en active Application Filing
- 2019-09-18 CN CN201980071319.4A patent/CN113164940B/en active Active
- 2019-09-18 KR KR1020217011226A patent/KR102588583B1/en active IP Right Grant
- 2019-09-18 KR KR1020217011227A patent/KR102588584B1/en active IP Right Grant
- 2019-09-18 CN CN201980069116.1A patent/CN112912176B/en active Active
- 2019-09-18 JP JP2021539330A patent/JP7480154B2/en active Active
- 2019-09-18 WO PCT/TH2019/000042 patent/WO2020060499A1/en active Application Filing
-
2021
- 2021-03-18 US US17/206,077 patent/US11938467B2/en active Active
- 2021-03-18 US US17/206,080 patent/US11938468B2/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| EP3852920A1 (en) | 2021-07-28 |
| US11938467B2 (en) | 2024-03-26 |
| CN113164940A (en) | 2021-07-23 |
| EP3852921C0 (en) | 2023-06-07 |
| CN112912176A (en) | 2021-06-04 |
| KR20210057803A (en) | 2021-05-21 |
| JP7480154B2 (en) | 2024-05-09 |
| US20210205798A1 (en) | 2021-07-08 |
| JP7500576B2 (en) | 2024-06-17 |
| US11938468B2 (en) | 2024-03-26 |
| WO2020060499A1 (en) | 2020-03-26 |
| KR102588584B1 (en) | 2023-10-12 |
| JP2022501192A (en) | 2022-01-06 |
| CN112912176B (en) | 2023-11-17 |
| JP2022501426A (en) | 2022-01-06 |
| KR102588583B1 (en) | 2023-10-12 |
| WO2020060498A1 (en) | 2020-03-26 |
| CN113164940B (en) | 2023-09-29 |
| US20210346877A1 (en) | 2021-11-11 |
| KR20210057804A (en) | 2021-05-21 |
| EP3852921B1 (en) | 2023-06-07 |
| EP3852920B1 (en) | 2022-09-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US11938468B2 (en) | Catalyst system for producing cyclic carbonates and method related thereto | |
| Liang et al. | Postsynthetic ionization of an imidazole-containing metal–organic framework for the cycloaddition of carbon dioxide and epoxides | |
| Luo et al. | Metallosalen‐based ionic porous polymers as bifunctional catalysts for the conversion of CO2 into valuable chemicals | |
| Calabrese et al. | Supported Polyhedral Oligomeric Silsesquioxane‐Based (POSS) Materials as Highly Active Organocatalysts for the Conversion of CO2 | |
| Wu et al. | Chemical fixation of CO 2 into cyclic carbonates catalyzed by bimetal mixed MOFs: the role of the interaction between Co and Zn | |
| Kim et al. | Synthesis of dimethyl carbonate from ethylene carbonate and methanol using immobilized ionic liquid on amorphous silica | |
| CN101474576B (en) | Catalytic system for synthesizing annular carbonic acid ester | |
| US20130035497A1 (en) | Method of manufacturing cyclic carbonate from carbon dioxide | |
| Zhang et al. | POSS and imidazolium-constructed ionic porous hypercrosslinked polymers with multiple active sites for synergistic catalytic CO 2 transformation | |
| Akbari et al. | Heterogenization of a green homogeneous catalyst: Synthesis and characterization of imidazolium ionene/Br–Cl–@ SiO2 as an efficient catalyst for the cycloaddition of CO2 with epoxides | |
| CN105315233B (en) | The production method of epoxy butane | |
| WO2020169035A1 (en) | Method for preparing alkylene carbonate from alkylene oxide and carbon dioxide | |
| Li et al. | A novel 2D zinc (II)-organic framework for efficient catalytic cycloaddition of CO2 with epoxides | |
| JP6900064B2 (en) | Sequence-controlled oligosiloxanes, their production methods and oligosiloxane synthesizers | |
| CN107199051B (en) | A kind of copper heterogeneous catalyst of pyridine coordination and preparation method thereof | |
| CN110152739B (en) | Porous organic compound of in-situ supported palladium nanoparticles, synthetic method and application | |
| EP2595745A1 (en) | Epoxidation process | |
| RU2013117809A (en) | METHOD FOR PRODUCING TRIGALOGENESILANE | |
| WO2011009934A1 (en) | Tris(1,2,3-triazol-4-yl)methane organometallic compounds as catalysts and processes using them. | |
| CN113200954B (en) | Preparation method of cyclic carbonate | |
| CN115318341A (en) | Imidazole functionalized bimetallic MOF heterogeneous catalyst and application thereof | |
| TW201920211A (en) | Preparation of fluorosilicon compounds | |
| JPWO2020060499A5 (en) | ||
| Yoon et al. | Cu (ii) Cl 2 containing bispyridine-based porous organic polymer support prepared via alkyne–azide cycloaddition as a heterogeneous catalyst for oxidation of various olefins | |
| US9593134B2 (en) | Complexes useful as active components in supported epoxidation catalysts |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: UNKNOWN |
|
| STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE |
|
| STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE |
|
| PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
| STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE |
|
| 17P | Request for examination filed |
Effective date: 20210409 |
|
| AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR |
|
| DAV | Request for validation of the european patent (deleted) | ||
| DAX | Request for extension of the european patent (deleted) | ||
| GRAP | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOSNIGR1 |
|
| STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: GRANT OF PATENT IS INTENDED |
|
| INTG | Intention to grant announced |
Effective date: 20220506 |
|
| GRAJ | Information related to disapproval of communication of intention to grant by the applicant or resumption of examination proceedings by the epo deleted |
Free format text: ORIGINAL CODE: EPIDOSDIGR1 |
|
| STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE |
|
| INTC | Intention to grant announced (deleted) | ||
| GRAP | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOSNIGR1 |
|
| STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: GRANT OF PATENT IS INTENDED |
|
| INTG | Intention to grant announced |
Effective date: 20221007 |
|
| GRAS | Grant fee paid |
Free format text: ORIGINAL CODE: EPIDOSNIGR3 |
|
| GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
| STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE PATENT HAS BEEN GRANTED |
|
| AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR |
|
| REG | Reference to a national code |
Ref country code: GB Ref legal event code: FG4D |
|
| REG | Reference to a national code |
Ref country code: CH Ref legal event code: EP Ref country code: AT Ref legal event code: REF Ref document number: 1573317 Country of ref document: AT Kind code of ref document: T Effective date: 20230615 |
|
| REG | Reference to a national code |
Ref country code: DE Ref legal event code: R096 Ref document number: 602019030715 Country of ref document: DE |
|
| U01 | Request for unitary effect filed |
Effective date: 20230607 |
|
| U07 | Unitary effect registered |
Designated state(s): AT BE BG DE DK EE FI FR IT LT LU LV MT NL PT SE SI Effective date: 20230614 |
|
| REG | Reference to a national code |
Ref country code: NO Ref legal event code: T2 Effective date: 20230607 |
|
| REG | Reference to a national code |
Ref country code: LT Ref legal event code: MG9D |
|
| U20 | Renewal fee paid [unitary effect] |
Year of fee payment: 5 Effective date: 20230828 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: ES Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20230607 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: NO Payment date: 20230927 Year of fee payment: 5 Ref country code: GB Payment date: 20230927 Year of fee payment: 5 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: RS Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20230607 Ref country code: HR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20230607 Ref country code: GR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20230908 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20230607 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IS Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20231007 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SM Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20230607 Ref country code: SK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20230607 Ref country code: RO Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20230607 Ref country code: IS Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20231007 Ref country code: CZ Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20230607 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: PL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20230607 |
|
| REG | Reference to a national code |
Ref country code: DE Ref legal event code: R097 Ref document number: 602019030715 Country of ref document: DE |
|
| PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
| STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
| REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
| 26N | No opposition filed |
Effective date: 20240308 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: MC Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20230607 |